CN103365132A

CN103365132A - Toner for electrostatic latent image development

Info

Publication number: CN103365132A
Application number: CN2013100881739A
Authority: CN
Inventors: 宫本英稔
Original assignee: Kyocera Document Solutions Inc
Current assignee: Kyocera Document Solutions Inc
Priority date: 2012-03-30
Filing date: 2013-03-19
Publication date: 2013-10-23
Anticipated expiration: 2033-03-19
Also published as: US9069270B2; EP2645168B1; EP2645168A1; US20130260309A1; JP2013228680A; CN103365132B

Abstract

The invention provides a toner for electrostatic latent image development, wherein the toner is advantaged by improved property. The toner containing a binder resin, a release agent, and pigment fine particles is produced by aggregating fine particles containing the components of the toner to obtain fine particle aggregates and then coalescing the fine particle aggregates. The pigment fine particles have an average primary particle diameter of 50 nm or less, a Cv value of less than 20%, and an average circularity of 0.900 or more.

Description

Developing toner for electrostatic latent images

Technical field

The present invention relates to developing toner for electrostatic latent images.

Background technology

Usually in xeroprinting, make after the surface charging of electrostatic latent image supporting body by corona discharge etc., form electrostatic latent image by exposures such as laser instruments, and form toner image by this electrostatic latent image of toner development, and then this toner image is transferred on the recording medium and obtains high-quality image.Usually the toner that is applicable to this xeroprinting uses the constituent of the toners such as mixed colorant, charge control agent, mould release and magnetic material in the binding resins such as thermoplastic resin and carries out mixing, pulverizing, classification and the toner particle below the 10 μ m more than the mean grain size 5 μ m that form.And, for giving flowability to toner, or carry out the band electric control of toner, or improve the purpose of the spatter property of toner, the inorganic micro powder outsides such as silicon dioxide or titanium dioxide are added in the toner.

About this toner, in recent years for the requirement to the higher image quality of formation image, require to dwindle the particle diameter of toner to improve resolution.In order to export the image of high image quality, preferably make about mean grain size path to the 5 μ m of toner, and make the toner size-grade distribution precipitous.

Therefore, binding resin, colorant and mould release etc. are included in after the particle coagulation of the composition in the toner, by heating make the condensed matter polymerization form toner the particle coagulation method because be easy to control the size-grade distribution of toner particle, shape and the dispersivenesses of composition in toner inside such as colorant and mould release of toner get most of the attention.The preparation method of existing a kind of toner, the method is for the particle coagulation method, be formulated in crystalline resin, colorant and mould release and be added with the dispersion liquid of the spreading agents such as methylcellulose, hydroxyethyl cellulose separately with in the potpourri of aqueous medium, and make after the composition cohesion that is included in the dispersion liquid, make the condensed matter polymerization of particulate obtain toner.

When utilizing the method for using above-mentioned specific dispersant, really can obtain the toner of small particle diameter.But the cohesion between the pigment particle easily occurs when in the operation that makes the particle coagulation that is grouped into by one-tenth such as binding resin, colorant and mould releases pigment being used as colorant in the method.Therefore, inhomogeneous by the condensed matter component of binding resin particulate, colorant particles and mould release ultrafine particles composition occurs easily in the method.When this composition inhomogeneous occured, the carried charge of resulting toner was distributed with and may broadens.In the case, when printing for a long time, may cause the image color of the image that forms to be lower than expectation value.

As the method for the coagulation problems that solves pigment particle, can consider when the preparation pigment particle, to add the dispersiveness that a large amount of dispersing aiies improves pigment particle.But at this moment, in the operation that makes the particle coagulation that is grouped into by one-tenth such as binding resin, colorant and mould releases, the cohesion of particulate partly is obstructed, and the particle diameter of resulting toner is distributed with and may broadens.In the case, because the surface area of toner particle is according to particle diameter and difference, so the distribution of the carried charge of toner also can broaden.

Summary of the invention

Developing toner for electrostatic latent images of the present invention comprises binding resin, pigment particle and mould release at least.Developing toner for electrostatic latent images of the present invention is by obtaining after the particle coagulation body particle coagulation that comprises the composition that consists of developing toner for electrostatic latent images, makes the polymerization of described particle coagulation body and obtains.The average primary particle diameter of described pigment particle is below the 50nm, and the Cv value is less than 20%, and average roundness is more than 0.900.

Description of drawings

Fig. 1 is the figure that the detection method of the softening point that uses high formula fluidity testing instrument (high formula フローテスタ) is described.

Fig. 2 is the cut-open view of the microreactor that uses in the preparation of dispersible pigment dispersion.

Embodiment

Below embodiments of the present invention are specifically described, carry out any restriction yet the present invention can't help following embodiment, in purpose range of the present invention, can suitably change to implement.And for the part of repeat specification, suitably description thereof is omitted sometimes, but be not to limit the invention main idea.

Developing toner for electrostatic latent images of the present invention comprises binding resin, mould release and pigment particle, and the average primary particle diameter of this pigment particle is below the 50nm, and the Cv value is less than 20%, and average roundness is more than 0.900.Developing toner for electrostatic latent images of the present invention is by obtaining after the particle coagulation body particle coagulation that comprises the composition that consists of developing toner for electrostatic latent images, makes the polymerization of described particle coagulation body and obtains.Next coming in order describe developing toner for electrostatic latent images of the present invention and the method for preparing developing toner for electrostatic latent images of the present invention.

" developing toner for electrostatic latent images "

Developing toner for electrostatic latent images of the present invention (following also referred to as toner) must comprise binding resin, pigment and mould release, and can also contain the compositions such as charge control agent and Magnaglo as required.Toner of the present invention can also have external additive in its surface attachment as required.Toner of the present invention can also mix with the carrier of expectation and use as two-component developing agent.Below, successively to as in the preparation of toner, use must or the binding resin, pigment, mould release, charge control agent, Magnaglo, external additive of material and the carrier of employing when toner is used as two-component developing agent describe arbitrarily.

[binding resin]

Binding resin is suitably selected from the resin that the binding resin of all the time using as toner uses.As the concrete example of binding resin, can enumerate the thermoplastic resins such as styrene resin, (methyl) acrylic resin, styrene-(methyl) acrylic resin, polythylene resin, polypropylene-based resin, vinyl chloride resin, vibrin, polyamide, urethane resin, polyvinyl alcohol resin, vinyl ether resinoid, the vinyl-based resin of N-, styrene-butadiene resin.

The part (end or side chain) that binding resin is preferably at strand has the resin such as carboxyl or sulfonic acidic-group, when using suitable preparation method described later to prepare toner, carries out well the cohesion of the particulate in the operation (I) like this.As this resin with acidic-group, can enumerate (methyl) acrylic resin, styrene-(methyl) acrylic resin and vibrin.Have in the resin of acidic-group at these, from the adjustment of fusing point and glass transition temperature easily, the toner, the colorant that are easy to formulating low-temperature fixation performance excellence be easy to consider preferred polyester resin aspect the well dispersion toner.

When binding resin is when having the resin of acidic-group, the acid value of binding resin is preferably below the above 40mgKOH/g of 5mgKOH/g.When using the excessively low binding resin of acid value to prepare toner, according to the prescription of operation described later (I), the cohesion of particulate is difficult to carry out well sometimes.When using the too high binding resin of acid value to prepare toner, under super-humid conditions, owing to be subject to humidity effect, might damage the various performances of gained toner.

Below for the resin with acidic-group, successively (methyl) acrylic resin, styrene-(methyl) acrylic resin and vibrin are described.

((methyl) acrylic resin)

(methyl) acrylic resin is the resin that is obtained by the monomer copolymerization that contains at least (methyl) acrylic monomer.The content of the unit that originates from (methyl) acrylic monomer that (methyl) acrylic resin comprises is preferably more than the 70 quality %, more preferably more than the 80 quality %, is particularly preferably more than the 90 quality %, most preferably is 100 quality %.

As (methyl) acrylic monomer that in the preparation of (methyl) acrylic resin, uses, can enumerate (methyl) acrylic acid; (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate and (methyl) propyl acrylate; (methyl) acrylamide, N-alkyl (methyl) acrylamide, N-aryl (methyl) acrylamide, N, N-dialkyl group (methyl) acrylamide and N, (methyl) acrylamide compounds such as N-diaryl ester (methyl) acrylamide.(methyl) acrylic resin preferably will originate from the carboxyl that comprises in (methyl) acrylic acid unit and comprise as acidic-group.At this moment, when preparation (methyl) acrylic resin, can adjust by increase and decrease (methyl) acrylic acid use amount the acid value of (methyl) acrylic resin.

When (methyl) acrylic resin during for resin that other monomer copolymerizations beyond (methyl) acrylic monomer are formed, as other monomers, can enumerate the olefines such as ethene, propylene, butene-1, amylene-1, hexene-1, heptene-1 and octene-1; The allyl ester classes such as allyl acetate, benzoic acid allyl ester, acetoacetic acid allyl ester and lactic acid allyl ester; Hexyl vinyl ether, octyl group vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl group vinyl ether, chloroethyl vinyl ether, 2-ethyl-butyl vinyl ether, dimethyl aminoethyl vinyl ether, diethylamino ethyl vinyl ether, benzyl vinyl ether, vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl-2, the vinethenes such as 4-dichlorophenyl ether and vinyl naphthyl ether; The vinyl acetate such as vinyl acetate, propionate, vinyl butyrate, isobutyric acid vinyl acetate, vinyl acetate base diethylester, vinyl chloroacetate, methoxyacetic acid vinyl acetate, butoxy acetic acid vinyl acetate, vinyl acetic acid phenyl ester, vinyl acetoacetic ester, lactic acid vinyl acetate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid ethene and naphthoic acid ethene.

(styrene-(methyl) acrylic resin)

Styrene-(methyl) acrylic resin is the resin that obtains with the monomer copolymerization of (methyl) acrylic monomer containing at least styrene monomer.The unit that originates from styrene monomer that contains in styrene-(methyl) acrylic resin is preferably more than the 70 quality % with the total of the content of the unit that originates from (methyl) acrylic monomer, more preferably more than the 80 quality %, be particularly preferably more than the 90 quality %, most preferably be 100 quality %.

As the styrene monomer that in the preparation of styrene-(methyl) acrylic resin, uses, can enumerate styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, 2,4-DMS, p-n-butylbenzene ethene, p-dodecyl styrene, p-methoxy styrene, p-styryl phenyl and p-chlorostyrene.

(methyl) acrylic monomer that uses in the preparation of styrene-(methyl) acrylic resin is same with (methyl) acrylic monomer that uses in the preparation of (methyl) acrylic resin.

Styrene-(methyl) acrylic resin preferably will be included in the carboxyl that originates from (methyl) acrylic acid unit and comprise as acidic-group.At this moment, when preparation styrene-(methyl) acrylic resin, can adjust by increasing and decreasing (methyl) acrylic acid use amount the acid value of styrene-(methyl) acrylic resin.

When resin that styrene-(methyl) acrylic resin obtains for other monomers beyond will (methyl) acrylic monomer and styrene monomer copolymerization, in the example of other monomers and (methyl) acrylic resin, (methyl) acrylic monomer other monomers in addition are same.

(vibrin)

Vibrin can use the resin that obtains by the method that adopts binary or the pure composition more than the ternary and binary or the carboxylic acid composition's polycondensation more than the ternary or copolycondensation.As the composition that uses when the synthesizing polyester resin, can enumerate following pure composition and carboxylic acid composition.

Concrete example as binary or the pure composition more than the ternary, can enumerate ethylene glycol, diglycol, triethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, neopentyl glycol, Isosorbide-5-Nitrae-butylene glycol, 1,5-PD, 1, the glycolss such as 6-hexanediol, 1,4-CHDM, dipropylene glycol, polyglycol, polypropylene glycol and polytetramethylene glycol; The bisphenols such as bisphenol-A, hydrogenated bisphenol A, polyoxyethylene bisphenol-A and polyoxypropylene bisphenol-A; D-sorbite, 1,2,3, the own tetrol of 6-, 1,4-sorbitan, pentaerythrite, dipentaerythritol, tripentaerythritol, BT, 1,2,5-penta triol, glycerine, two glycerine, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-butantriol, trimethylolethane, trimethylolpropane and 1, the alcohols that the ternarys such as 3,5-trihydroxytoluene are above.

Concrete example as binary or the carboxylic acid composition more than the ternary, can enumerate maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), cyclohexane dicarboxylic acid, succinic acid, hexane diacid, decanedioic acid, azelaic acid, 1,10-dicarboxylic acid in the last of the ten Heavenly stems, malonic acid, perhaps normal-butyl succinic acid, n-butene base succinic acid, the isobutyl succinic acid, the isobutenyl succinic acid, the n-octyl succinic acid, positive ocentyl succinic, the dodecyl succinic acid, positive dodecene base succinic acid, the dicarboxylic acids such as alkyl or alkenyl succinic acid such as Permethyl 99A base succinic acid and different dodecene base succinic acid; 1,2,4-benzene tricarbonic acid (trimellitic acid), 1,2,5-benzene tricarbonic acid, 2,5,7-naphthalene tricarboxylic acids, 1,2,4-naphthalene tricarboxylic acids, 1,2,4-butane tricarboxylic acids, 1,2,5-hexane tricarboxylic acids, 1,3-dicarboxyl-2-methyl-2-methylene carboxyl propane, 1,2,4-cyclohexane tricarboxylic acids, four (methylene carboxyl) methane, 1,2,7,8-octane tetrabasic carboxylic acid, pyromellitic acid and empol(エンポー Le) the above carboxylic acid of the ternary such as trimer acid etc.The above carboxylic acid composition of these binary or ternary can also be used as the derivant of the ester formatives such as acyl halide, acid anhydrides and lower alkyl esters.Wherein, " low alkyl group " to refer to carbon number be 1 to 6 alkyl.

The acid value of vibrin can become the balance of these functional groups of carboxyl that hydroxyl that branch has and carboxylic acid composition have to adjust by being adjusted at the alcohol of using in vibrin synthetic.

As binding resin described above, consider from the good aspect of fixation performance, preferably use thermoplastic resin, yet not only can use separately thermoplastic resin, can also in thermoplastic resin, add crosslinking chemical or heat-curing resin.By in binding resin, importing a part of cross-linked structure, can not reduce fixation performance, can improve the performance of the toners such as storage stability, shape keeping property and permanance.

Heat-curing resin as using with thermoplastic resin for example is preferably epoxy resin or cyanate resin.As the concrete example of preferred heat-curing resin, can enumerate the resins such as bisphenol A type epoxy resin, bisphenol-A epoxy resin, phenol aldehyde type epoxy resin, polyalkylene ether type epoxy, annular aliphatic type epoxy resin and cyanate ester resin.These heat-curing resins can make up two or more the use.

The softening point of binding resin is preferably more than 80 ℃ below 150 ℃, more preferably more than 90 ℃ below 140 ℃.When use contains the toner of the too high binding resin of softening point, sometimes be difficult at low temperatures make well photographic fixing of toner.When use contains the toner of the excessively low binding resin of softening point, can make the toner cohesion when at high temperature preserving, and the heat-resisting keeping quality of infringement toner.The softening point of binding resin can be measured according to following method.

＜softening point measurement method 〉

Use high formula fluidity testing instrument (CFT-500D, Shimadzu Scisakusho Ltd's system) to carry out the mensuration of the softening point of binding resin (toner).Use the toner of 1.5g as sample, uses height to be 1.0mm and the diameter punch die as 1.0mm, at 4 ℃/min of programming rate, 300 seconds preheating time, load-carrying 5kg measures under the condition that the mensuration temperature range is 60～200 ℃.According to the temperature that is obtained by the mensuration of using the fluidity testing instrument (℃) the S type curve relevant with stroke (mm), read softening point.

By Fig. 1 the read method of softening point is described.The maximal value of stroke is made as S1, the stroke value of the baseline of low temperature side is made as S2.In S type curve, the value of stroke is made as the softening point of working sample for the temperature of (S1+S2)/2.

The glass transition temperature of binding resin (Tg) is preferably more than 50 ℃ below 70 ℃.When use comprises the toner of the excessively low binding resin of Tg, since the strength decreased of toner particle integral body, the cohesion that under the many wet environments of high temperature, produces sometimes toner particle.When use comprises the toner of the too high binding resin of Tg, sometimes be difficult at low temperatures make well photographic fixing of toner.

The assay method of＜glass transition temperature (Tg) 〉

The glass transition temperature of binding resin can be tried to achieve according to the assay method of foundation JIS K7121.More specifically, the differential scanning calorimeter DSC-6200 processed of Jinggong Co., Ltd (セイコーイ Application ス Star Le メ Application Star Co., Ltd.) can be measured the endothermic curve of binding resin as determinator and try to achieve the glass transition temperature of binding resin.Can be by passing through in the aluminium dish, to add working sample 10mg, as the aluminium dish with reference to the use sky, and measuring under 25～200 ℃ of temperature ranges, the 10 ℃/min of programming rate, the endothermic curve of measuring the binding resin that obtains under ambient temperature and moisture is tried to achieve the glass transition temperature of binding resin.

The number-average molecular weight Mn of binding resin is preferably more than 3000 below 20000, more preferably more than 5000 below 15000.The molecular weight distribution mw/mn that is represented by the ratio of number-average molecular weight Mn and matter average molecular weight Mw is preferably more than 2 below 60, more preferably more than 2 below 10.When being located at the molecular weight distribution of binding resin in the above-mentioned scope, be easy to the generation that suppresses to be offset, in addition, be easy to do not produced the wide toner of temperature range of skew.The number-average molecular weight Mn of binding resin and matter average molecular weight Mw can use gel permeation chromatography to measure.

[pigment]

The pigment that contains in developing toner for electrostatic latent images can cooperate the color of toner particle to use known pigment.As the concrete example that can add the suitable pigment in the toner to, can enumerate following pigment.

As yellow colorants, can enumerate the colorants such as condensation azo-compound, isoindoline ketonic compound, anthraquinone compounds, azo metal complex, methylidyne compound and allyl amide compound.Particularly, can enumerate C.I. pigment yellow 3,12,13,14,15,17,62,74,83,93,94,95,97,109,110,111,120,127,128,129,147,151,154,155,168,174,175,176,180,181,191,194; The colorants such as naphthol yellow S, hansa yellow G and C.I. vat yellow.

As magenta coloring agent, can enumerate condensation azo-compound, pyrrolo-pyrrole-dione compound, anthraquinone compounds, quinacridone compound, basic-dyeable fibre color lake compound, naphthol compound, benzimidazolone compound, thioindigo compound with and the colorant such as perylene compound.Particularly, can enumerate C.I. paratonere 2,3,5,6,7,19,23,48:2,48:3,48:4,57:1,81:1,122,144,146,150,166,169,177,184,185,202,206,220, the colorants such as 221 and 254.

As cyan colorant, can enumerate the colorants such as copper phthalocyanine compound, copper phthalocyanine derivative thing, anthraquinone compounds and basic-dyeable fibre color lake compound.Particularly, can enumerate C.I. pigment blue 1,7,15,15:1,15:2,15:3,15:4,60,62 and 66; The colorants such as phthalocyanine blue, C.I. vat blue and C.I. acid blue.

The use amount of colorant is preferably below above 30 mass parts of 1 mass parts with respect to binding resin 100 mass parts.

[mould release]

Developing toner for electrostatic latent images contains mould release to improve fixation performance and anti-skew as purpose.If the kind that the mould release that the kind of mould release is used as toner all the time uses then without particular limitation of.

As suitable mould release, can enumerate aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low-molecular-weight polypropylene, polyolefin copolymer, polyolefin-wax, microcrystalline wax, paraffin and the general uncommon synthetic wax of Fei Xier-Toro; The oxide of the aliphatic hydrocarbon waxes such as segmented copolymer of oxidized polyethlene wax and oxidized polyethlene wax; The plant waxes such as candelila wax, Brazil wax, vegetable wax, Jojoba wax and rice bran wax; The animal class waxes such as beeswax, sheep oil and spermaceti; The mineral substance waxes such as ceresine, ceresin and vaseline; Wax class take fatty acid esters such as montanic acid ester type waxes and castor wax as major component; Deoxidation Brazil wax etc. makes the part of fatty acid ester or the wax of integral deoxidation.

The use amount of mould release is preferably below above 20 mass parts of 1 mass parts with respect to binding resin 100 mass parts, more preferably below above 15 mass parts of 5 mass parts.

[charge control agent]

Developing toner for electrostatic latent images can also contain charge control agent as required.Can charge control agent make the at short notice charged rising characteristic of the index of charged charged level to stipulating of toner with the charged stabilization of level that improves toner with becoming, and the toner that obtains permanance and excellent in stability is that purpose is used.When the toner positively charged is developed, use the charge control agent of positively charged, when making that toner is electronegative to develop, use the charge control agent of electronegative property.

Charge control agent can suitably be selected from the charge control agent that is used for toner all the time.As the concrete example of the charge control agent of positively charged, can enumerate pyridazine, pyrimidine, pyrazine Lin oxazine Jian oxazine paroxazine, orthothiazine, between thiazine, parathiazine, 1,2, the 3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2, the 4-oxadiazine, 1,3,4-oxadiazine, 1,2,6-oxadiazine, 1,3, the 4-thiadiazine, 1,3,5-thiadiazine, 1,2,3,4-tetrazine, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,4,6-Evil triazine, 1,3,4,5-Evil triazine, phthalazines, the azines such as quinazoline and quinoxaline, azine fast red FC, azine fast red 12BK, the purple BO of azine, azine palm fibre 3G, the shallow brown GR of azine, the dark green BH/C of azine, the pitch black EW of azine and the pitch black 3RL of azine etc. contain the direct dyes of azines, nigrosine, the nigrosine compounds such as aniline black salt and nigrosine derivant; The acid dyes that is consisted of by nigrosine compounds such as nigrosine BK, nigrosine NB and nigrosine Z; The metallic salt of naphthenic acid or higher fatty acid; Alkoxylated amines; Alkylamide; The quaternary ammonium salts such as benzyl methyl hexyl decyl ammonium and decyl trimethyl ammonium chloride.In the charge control agent of these positively chargeds, from obtaining more rapidly charged rising aspect consideration, be particularly preferably the nigrosine compound.The charge control agent of these positively chargeds can make up two or more the use.

As functional group, the resin with quaternary ammonium salt, carboxylate or carboxyl also can be as the charge control agent of positively charged.More specifically, can enumerate the styrene resin with quaternary ammonium salt, acrylic resin with quaternary ammonium salt, styrene-propene acid resin with quaternary ammonium salt, polyester resin with quaternary ammonium salt, styrene resin with carboxylate, acrylic resin with carboxylate, styrene-propene acid resin with carboxylate, polyester resin with carboxylate, styrene resin with carboxyl, acrylic resin with carboxyl, have the styrene-propene acid resin of carboxyl and have in the polyester resin of carboxyl one or more.The molecular weight of these resins in the scope that does not hinder the object of the invention without particular limitation of, can be oligomer or polymkeric substance.

As the concrete example of the charge control agent of electronegative property, can enumerate metal-organic complex and chelate.As metal-organic complex and chelate, be preferably the acetylacetone metal complex and 3 such as aluminium acetylacetonate and diacetone ferrous iron, salicylic acid metal complex or the salicylic acid slaines such as 5-di-tert-butyl salicylic acid chromium, more preferably salicylic acid metal complex or salicylic acid slaine.The charge control agent of these electronegative property can make up two or more the use.

When the toner total amount is 100 mass parts, the consumption of the charge control agent of positively charged or electronegative property is preferably below above 15 mass parts of 1.5 mass parts, more preferably below above 8.0 mass parts of 2.0 mass parts, be particularly preferably below above 7.0 mass parts of 3.0 mass parts.When the very few toner of the content that uses charge control agent, owing to be difficult to make stably charged polarity to regulation of toner, therefore the image color of the image that forms is lower than expectation value or is difficult to keep for a long time image color.In addition, in the case, charge control agent is difficult to disperse equably the pollution that the image that forms is easy to produce photographic fog or easily causes latent image carrier section in binding resin.When the too much toner of the content that uses charge control agent, be easy to cause that image in the image is bad, the problems such as pollution of latent image carrier section because charged bad under hot and humid of resulting from of causing of environment resistant deterioration forms.

[Magnaglo]

Can cooperate Magnaglo as required in the developing toner for electrostatic latent images.As the example of suitable Magnaglo, can enumerate the iron such as ferrite and magnetic iron ore; The ferromagnetic metal such as cobalt, nickel contains the alloy of iron and/or ferromagnetic metal; The compound that contains iron and/or ferromagnetic metal; Implemented the ferromagnetic alloy of the ferromagnetism processing such as thermal treatment; And chromium dioxide.

The particle diameter of Magnaglo is preferably below the above 1.0 μ m of 0.1 μ m, more preferably below the above 0.5 μ m of 0.1 μ m.When the Magnaglo of the particle diameter that uses above-mentioned scope, Magnaglo is evenly dispersed in the binding resin.

For the purpose of the dispersiveness of improving the Magnaglo in the toner, can also use by surface conditioning agents such as titanium class coupling agent or silane coupling agents and carry out the surface-treated Magnaglo.

When toner is used as monocomponent toner, be in the situation of 100 mass parts in the toner total amount, the use amount of Magnaglo is preferably below above 60 mass parts of 35 mass parts, more preferably below above 60 mass parts of 40 mass parts.When the too much toner of the content that uses Magnaglo, be difficult to keep for a long time image color or be difficult to make securely photographic fixing of toner image.When the very few toner of the content that uses Magnaglo, the image that forms easily produces photographic fog or is difficult to keep for a long time image color.When toner is used as two-component developing agent, be in the situation of 100 mass parts in the toner total amount, the use amount of Magnaglo is preferably below the 20 quality %, more preferably below the 15 quality %.

[external additive]

The developing toner for electrostatic latent images that uses method of the present invention to obtain can be processed its surface by external additive as required.The kind of external additive in the scope that does not hinder the object of the invention without particular limitation of, can suitably select from the external additive that is used for toner all the time.As the concrete example of suitable external additive, can enumerate the metal oxides such as silicon dioxide, aluminium oxide, titanium dioxide, magnesium oxide, zinc paste, strontium titanates and barium titanate.These external additives can make up two or more the use.

The particle diameter of external additive is preferably below the above 1.0 μ m of 0.01 μ m.

The use amount of external additive is added front toner particle 100 mass parts of processing with respect to the outside, is preferably below above 10 mass parts of 0.1 mass parts, more preferably below above 5 mass parts of 0.2 mass parts.

[carrier]

The developing toner for electrostatic latent images that uses method of the present invention to obtain can also mix as two-component developing agent with the carrier of expectation.When the preparation two-component developing agent, preferably use magnetic carrier.

As the suitable carrier during as two-component developing agent with developing toner for electrostatic latent images, can enumerate the carrier that the carrier core is formed by resin-coating.As the concrete example of carrier core, can enumerate the metallicss such as iron, oxidation processes iron, reduced iron, magnetic iron ore, copper, silicon steel, ferrite, nickel and cobalt; The alloy particle of the metals such as these materials and manganese, zinc and aluminium; The alloy particle such as Fe-Ni alloy and iron-cobalt-base alloy; The ceramic particles such as titanium dioxide, aluminium oxide, cupric oxide, magnesium oxide, massicot, zirconia, silit, magnesium titanate, barium titanate, lithium titanate, lead titanates, lead zirconates and lithium niobate; The particle of the high-k materials such as ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate and Rochelle salt; And the resin carrier that in resin, is dispersed with above-mentioned magnetic particle.

As the concrete example of the resin of coated carrier core, can enumerate (methyl) acrylic polymers, styrenic polymer, styrene-(methyl) acrylic copolymer, olefin polymer (tygon, haloflex and polypropylene), Polyvinylchloride, polyvinyl acetate, polycarbonate, celluosic resin, vibrin, unsaturated polyester resin, polyamide, urethane resin, epoxy resin, silicone resin, fluororesin (teflon, polychlorotrifluoroethylene and polyvinylidene fluoride), phenolics, xylene resin, diallyl phthalate ester resin, polyacetal resin and amino resins.These resins can make up two or more the use.

For the particle diameter of carrier, use the particle diameter of determination of electron microscopy to be preferably below the above 120 μ m of 20 μ m, more preferably below the above 80 μ m of 25 μ m.

When developing toner for electrostatic latent images of the present invention was used as two-component developing agent, the content of toner was preferably below the above 20 quality % of 3 quality % with respect to the quality of two-component developing agent, more preferably below the above 15 quality % of 5 quality %.When the content of the toner in the two-component developing agent is above-mentioned scope, can continue to form the image of appropriate image color, and pollution and toner the adhering at transfer paper that can disperse to suppress image processing system inside from developing apparatus by suppressing toner.

Use material described above, and use the method for following explanation to prepare developing toner for electrostatic latent images.

" preparation method of developing toner for electrostatic latent images "

Developing toner for electrostatic latent images of the present invention is by obtaining after the particle coagulation body particle coagulation that comprises the composition that consists of developing toner for electrostatic latent images, makes the polymerization of described particle coagulation body and obtains.Developing toner for electrostatic latent images of the present invention preferably uses and comprises at least following operation (I) and the preparation of method (II).

(I) with following (A) and (B), namely

(A) comprise that at least volume average particle size is the binding resin dispersion liquid of the following binding resin particulate of 1.0 μ m and comprise that at least volume average particle size is the mould release dispersion liquid of the following mould release particulate of 1.0 μ m, perhaps

At least comprise and contain the binding resin composition dispersion liquid that volume average particle size is the particulate of the following binding resin of 1.0 μ m and mould release; And

(B) contain the dispersible pigment dispersion of pigment particle

Be mixed to get after the aqueous medium dispersion liquid of particulate, make particle coagulation and obtain containing the cohesion process of aqueous medium dispersion liquid of the particle coagulation body of binding resin, colorant and mould release; And

(II) the aqueous medium dispersion liquid of particle coagulation body is carried out the shape control operation of heat treated.

The preparation method of developing toner for electrostatic latent images of the present invention uses and comprises average primary particle diameter as below the 50nm, and the Cv value is less than 20%, and average roundness is the dispersible pigment dispersion of the pigment particle more than 0.900.Comprise that the compound method of pigment particle dispersion liquid of the pigment particle with this average primary particle diameter, Cv value and average roundness is without particular limitation of, but the preferred method of using the microreactor preparation of following explanation.

Particularly,

The preferred employing mixed the first pigment stoste and the second pigment stoste and made pigment separate out the method for pigment preparation particle dispersion liquid by microreactor, and wherein microreactor comprises:

Shaft collar A and rotating disc B for discoid two dishes, are configured to form thin layer between the circular face of two dishes;

The first stoste supply unit is supplied with the first pigment stoste from the end of described thin layer to described thin layer; And

At least one second stoste supply unit, take the center of the circular face of described shaft collar as benchmark, at the opposition side of described the first stoste supply unit, be communicated with the upper surface of described shaft collar and lower surface and form, and be used for supplying with the second pigment stoste from the upper surface side of described shaft collar to described thin layer.

Since developing toner for electrostatic latent images of the present invention with comprise that average primary particle diameter 50nm is following, the Cv value less than 20%, average roundness is that the pigment particle dispersion liquid of the pigment particle more than 0.900 prepares, therefore shape is even, and particle diameter distributes and carried charge distributes precipitous.

The preparation method who comprises above-mentioned operation (I) and developing toner for electrostatic latent images (II) can also comprise following operation (III)～(V) as required.

(III) matting of toner of shape that has been used for cleaning control.

(IV) drying process of toner of shape that has been used for drying control.

(V) external additive is attached to controlled the outside of the toner surface of shape to add operation.

Next coming in order describe the operation of (I)～(V).

[(I) cohesion process]

In (I) cohesion process, at first will

The binding resin dispersion liquid that comprises at least the binding resin particulate that volume average particle size 1.0 μ m are following, and

The mould release dispersion liquid that comprises at least the mould release particulate that volume average particle size 1.0 μ m are following, perhaps

The binding resin composition dispersion liquid that comprises at least the particulate that contains binding resin and mould release that volume average particle size 1.0 μ m are following; And

Comprise that average primary particle diameter, Cv value and average roundness are after the dispersible pigment dispersion of pigment particle of specialized range value, make the particle coagulation that is included in the mixed liquor.The method that in aqueous medium, makes particle coagulation without particular limitation of.Next coming in order describe the preparation of particulate and the cohesion of particulate.

(preparation of particulate)

The compound method of the dispersion liquid except dispersible pigment dispersion that in operation (I), uses without particular limitation of.Usually, the dispersion liquid that comprises the particulate of these compositions is prepared as composition in aqueous medium is turned to the particulate of required size by particulate aqueous medium dispersion liquid.Below for the various compositions that contain in the particulate, the compound method of particle dispersion liquid is described.

(comprising the preparation of the binding resin composition dispersion liquid of the particulate that contains binding resin and mould release)

Below the compound method of the binding resin composition dispersion liquid that comprises the particulate that contains binding resin and mould release is described.

At first, use the mixing arrangement such as Henschel mixer (ヘ Application シェ Le ミキサー, Mitsui Mining Co Ltd. BJ Offc's system) that the compositions such as binding resin, mould release, the charge control agent that comprises as required and Magnaglo are mixed.Then, the gained potpourri is used the evenly mixing device melting mixings such as biaxial extruder, three roller mixing machines or two roller mixing machines, thereby obtain binding resin composition.Cool off after the resulting binding resin composition, use the reducing mechanisms such as shredding machine (カッターミ Le), intermediate crusher (Off ェザーミ Le) or airslide disintegrating mill (ジェットミ Le) that binding resin composition is carried out coarse crushing.The particle diameter of the binding resin composition during coarse crushing is preferably below the 30 μ m.

Make the coarse crushing product of binding resin composition be dispersed in the dispersion liquid that obtains binding resin composition in the aqueous medium.By dispersion liquid being heated to the high temperature more than 10 ℃ of softening point than the binding resin of being measured by flow tester, and use homogenizer or pressure spray type dispersion machine to apply powerful shearing force to the dispersion liquid of the binding resin composition after the heating, thereby obtain comprising the aqueous medium dispersion liquid of the particulate of binding resin that volume average particle size 1.0 μ m are following and mould release.

As the device that dispersion liquid is applied powerful shearing force, can enumerate the U.S. grain system of NANO3000(Co., Ltd.), nanometer machine (Na ノマイザー, the industrial Co., Ltd. of Jitian's machinery system), Microfluidiser(マイ Network ロ Off Le ダイザー, MFI company system), Gaulin Homogenizer(ゴーリ Application ホモジ Na イザー, マ Application トンゴーリ Application company system) and CLEARMIX W motion(Network レアミッ Network ス W モーショ Application, エ system テ Network ニッ Network Co., Ltd. system) device such as.

The volume average particle size D50 that uses the particulate that comprises binding resin and mould release of said method preparation is made as 1.0 μ m when following, is easy to prepare shape evenly and the precipitous developing toner for electrostatic latent images of particle diameter distribution.Accordingly, can also stablize performance and the production efficiency of toner.Comprise that the volume average particle size D50 of particulate of binding resin and mould release is more preferably below the above 0.5 μ m of 0.1 μ m.When the volume average particle size D50 that will comprise the particulate of binding resin and mould release is located in this scope, can further bring into play above-mentioned effect.

Aqueous medium is so long as the liquid medium take water as major component, then in the scope that does not hinder the object of the invention without particular limitation of.The water that contains in the aqueous medium can suitably be selected from the water such as tap water, process water, distilled water and ion exchange water.

Aqueous medium can also contain organic solvent in the scope that does not hinder the object of the invention.The amount of the organic solvent when aqueous medium comprises organic solvent is preferably below the 20 quality % with respect to the quality of aqueous medium, is preferably below the 10 quality %, is preferably below the 5 quality %.As the organic solvent that can in aqueous medium, comprise, can enumerate ketone, the N such as the ethers such as the alcohols such as methyl alcohol and ethanol, tetrahydrofuran, acetone, the nitrogenous polar organic solvents such as dinethylformamide, DMA and METHYLPYRROLIDONE.

With respect to the use amount of the aqueous medium of binding resin composition if the micronize of binding resin composition carry out well then without particular limitation of.With respect to the use amount of the aqueous medium of binding resin composition according to the kind of the device of the preparation that is used for particulate and difference, but 1 quality that typically is preferably the binding resin composition quality doubly above 5 quality doubly below, more preferably doubly above 4 quality of 2 quality doubly below.

Preferably in aqueous medium, add surfactant.When adding surfactant in aqueous medium, the micronize of binding resin composition is carried out well, the dispersion liquid of the particulate of the dispersion stabilization excellence that is easy to get.

The surfactant that can be in aqueous medium uses in the preparation of particulate without particular limitation of, can from the group that anionic species surfactant, cationic surfactant and non-ionic surfactant consist of, suitably select.As the example of anionic species surfactant, can enumerate sulfated surfactant, sulfonate surfactant and soap (Shi Soap).As the example of cationic surfactant, can enumerate amine salt cationic surfactant and quaternary ammonium salt cationic surfactant.As the example of non-ionic surfactant, can enumerate polyethylene glycol type surfactant, alkylphenol ethylene oxide adduct type surfactant and higher alcohol type surfactant.In these surfactants, preferably use at least a in anionic species surfactant and the non-ionic surfactant.These surfactants can use a kind of, also can make up two or more the use.

As the anionic species surfactant, preferred polyoxyethylene alkyl ether sulfate salt.In polyoxyethylene alkyl ether sulfate salt, the material that is preferably represented by following formula (1).

R1-O-（CH ₂CH ₂O）p-SO ₃M…（1）

(in the formula (1), R1 is alkyl, and M is monovalent cation, and p is the integer below 50 more than 1.）

R1 can be straight chained alkyl, also can be branched alkyl, is preferably straight chained alkyl.R1 can also have unsaturated link.The carbon number of R1 is preferably more than 10 below 20, more preferably more than 12 below 18.P is the integer below 50 more than 1.Consider that from the aspect that the particle diameter that is easy to particulate is controlled in the suitable scope p is preferably the integer below 30 more than 1, more preferably the integer below 20 more than 2.M is monovalent cation.Consider that from the aspect that the particle diameter that is easy to particulate is controlled in the suitable scope M is preferably sodion, potassium ion or ammonium ion, more preferably sodion or ammonium ion are particularly preferably sodion.

Above-mentioned polyoxyethylene alkyl ether sulfate salt preferably uses with non-ionic surfactant.Non-ionic surfactant as using in the case carries out well from the micronize of colored resin composition, and the aspect of dispersion liquid that is easy to obtain the particulate of dispersion stabilization excellence considers, preferably uses polyoxyethylene alkyl ether.

When using surfactant, the concentration of the surfactant in the aqueous medium is preferably below the above 5.0 quality % of 0.5 quality %.

When binding resin is when having the resin of acidic-group; owing to directly in aqueous medium, make the binding resin micronize; therefore the specific surface area of binding resin increases; so be subject to being exposed to the impact of the acidic-group of microparticle surfaces, the scope about the pH of aqueous medium drops to more than 3 below 4 sometimes.In the case, produce sometimes as the hydrolysis of the vibrin of binding resin or be difficult to make the particle diameter micronize of gained particulate to required particle diameter.

In order to suppress the problems referred to above, when preparation comprises the binding resin composition dispersion liquid of the particulate that contains binding resin and mould release, preferably in aqueous medium, add alkaline matter.As long as alkaline matter can suppress the problems referred to above then without particular limitation of, but such as enumerating the alkali metal hydroxides such as NaOH, potassium hydroxide and lithium hydroxide; The alkali carbonate such as sodium carbonate and sal tartari; The alkali metal hydrogencarbonate such as sodium bicarbonate and saleratus; N, N-dimethylethanolamine, N, the nitrogenous organic bases such as N-diethyl ethanolamine, triethanolamine, tripropanol amine, three butanolamines, triethylamine, n-propylamine, n-butylamine, isopropylamine, single carbinolamine, morpholine, METHOXY PROPYL AMINE, pyridine and vinylpyridine.

As additive method, after can also being dissolved in the suitable solvent by the binding resin composition that will use the said method preparation, use the device such as homogenizer in the aqueous medium that has added surfactant, to disperse and the solution of emulsification binding resin composition, carry out afterwards the desolventizing processing and prepare the aqueous medium dispersion liquid of the particulate that comprises binding resin and mould release.

The particulate that comprises binding resin and mould release can also be prepared with the method that is called as so-called phase conversion emulsifying.Particularly, use following method, obtain comprising the particulate of binding resin and mould release.

At first, be dissolved in the binding resin composition that uses said method to obtain in the suitable solvent after, in the solution that obtains, add alkaline matter and carry out neutralisation treatment.Add water and make it after the phase inversion in the solution that has neutralized, the limit adds the thermal agitation limit and carries out desolventizing, thereby can prepare the aqueous medium dispersion liquid of the particulate that comprises binding resin and mould release.

(comprising the preparation of the binding resin composition dispersion liquid of the particulate that contains binding resin)

As mentioned above the compound method of the binding resin composition dispersion liquid that comprises the particulate that contains binding resin and mould release is illustrated, yet comprise binding resin particulate (not comprising mould release) dispersion liquid except binding resin not with the components matching of mould release, also can similarly prepare with said method.When binding resin is the resin of addition polymerization type, use following method also can prepare the binding resin composition dispersion liquid that comprises the particulate that contains binding resin.Particularly, when binding resin is the resin of the addition polymerization types such as (methyl) acrylic resin and styrene (methyl) acrylic resin, can prepare the particulate that comprises binding resin with as the aqueous medium dispersion liquid by prepare these resins with emulsion polymerization method.

(comprising the preparation of the mould release dispersion liquid of mould release particulate)

With the mould release coarse crushing be in advance below the 100 μ m about.The coarse crushing product of mould release are added in the aqueous medium that comprises surfactant, its slurry is heated to the temperature more than the fusing point of mould release.Use homogenizer or pressure spray type dispersion machine to apply powerful shearing force to the slurry that has heated, preparation comprises the dispersion liquid of the particulate of mould release.

The fusing point of mould release mostly is below 100 ℃ usually, and can under atmospheric pressure be heated to more than the fusing point this moment, and realize the micronize of mould release with common homogenizer.When the fusing point of mould release surpasses 100 ℃, can carry out micronize by using the pressure resistant type device, thereby realize the micronize of mould release.

The volume average particle size D50 that is included in the mould release particulate in the mould release dispersion liquid is preferably below the 1.0 μ m.When the volume average particle size D50 of mould release particulate is 1.0 μ m when following, it is even to prepare easily shape, the particle diameter precipitous developing toner for electrostatic latent images that distributes.The volume average particle size D50 of mould release particulate is more preferably below the above 0.5 μ m of 0.1 μ m.Can in the scope of grade, further bring into play above-mentioned effect by the volume average particle size D50 that makes the mould release particulate.

(comprising the preparation of the dispersible pigment dispersion of pigment particle)

The average primary particle diameter that is included in the pigment particle in the dispersible pigment dispersion is below the 50nm, and the Cv value is less than 20%, and average roundness is more than 0.900.Comprise this pigment particle dispersible pigment dispersion manufacture method without particular limitation of, yet be preferably the method for using aforesaid microreactor to prepare.

Dispersible pigment dispersion is by mixing from the first stoste supply unit the first pigment stoste of supplying with and the second pigment stoste of supplying with from the second stoste supply unit in microreactor and making pigment separate out preparation.Below use Fig. 2, the preparation with the dispersible pigment dispersion that uses microreactor describes to microreactor.

＜microreactor 〉

Fig. 2 is the diagrammatic cross-section of the microreactor that uses in the preparation of the dispersible pigment dispersion that comprises pigment particle.As shown in Figure 2, microreactor has two discoid dish-shaft collar A and rotating disc B.Shaft collar A and rotating disc B are configured to form betwixt thin layer.The thickness of thin layer is preferably below the above 100 μ m of 1 μ m.

Microreactor shown in Figure 2 uses the shaft collar A of movable floating structure on the direction parallel with turning axle c.The direction that pushes away shaft collar A up (being upward direction Fig. 2) pressure of effect, the deadweight of shaft collar A that the thickness of the thin layer that therefore, is formed by shaft collar A and rotating disc B can produce by the inflow by the first pigment stoste of supplying with from the first stoste supply unit and direction (lower direction among Fig. 2) applied pressure that presses solidly price fixing A are down adjusted.That is the flow that the thickness of the thin layer that, is formed by shaft collar A and rotating disc B can be by adjusting the first pigment stoste, the quality of shaft collar A and/or the back pressure that shaft collar A applies is adjusted from the upside of shaft collar A.As from the pressure of upside to shaft collar A effect, can enumerate the back pressure of using gas exerts.

The material of shaft collar A and rotating disc B if for be difficult for to produce the corrosion that the first pigment stoste and the second pigment stoste causes and the material with abundant intensity then without particular limitation of.As the example of the material of shaft collar A and rotating disc B, such as enumerating the materials such as carbon and silit, perhaps consider from the excellent aspect of resistance to chemical reagents, can enumerate the materials such as Hastelloy, glass, pottery and fluororesin.

The thickness that is formed on the thin layer between shaft collar A and the rotating disc B is preferably adjusted according to the kind of the first pigment stoste, the second pigment stoste and the pigment particle of separating out.The thickness of the thin layer when the pigment preparation dispersion liquid more preferably more than the 0.5 μ m below the 50 μ m, is particularly preferably below the above 10 μ m of 1 μ m.

Rotating disc B is rotated centered by the turning axle c at the center by shaft collar A and rotating disc B.The rotational speed of rotating disc B without particular limitation of, but when preparation comprises the dispersible pigment dispersion of pigment particle, be preferably below the above 4000rpm of 200rpm, more preferably below the above 3600rpm of 300rpm.

The quantity that is arranged at the second stoste supply unit y of shaft collar A can be one, also can be for a plurality of.When the quantity of the second stoste supply unit y when being a plurality of, the second pigment stoste of supplying with from the second stoste supply unit can for a kind of also can be for multiple.The shape of the second stoste supply unit y considers that the quantity delivered of the second pigment stoste suitably designs.

By using microreactor described above, can prepare shape evenly and the precipitous pigment particle of particle diameter distribution.As the microreactor that possesses said structure, force film reactor (ULREA SS-11(エ system テ Network ニッ Network Co., Ltd. system) such as enumerating) etc. device.Below the preparation of the dispersible pigment dispersion that comprises pigment particle that uses microreactor is described.

(using the preparation of the dispersible pigment dispersion of microreactor)

In the preparation of the dispersible pigment dispersion that uses microreactor, at first, as shown in Figure 2, supply with the first pigment stoste from the first stoste supply unit x, be formed on the space between shaft collar A and the rotating disc B and form the film fluid with the filling of the first pigment stoste.Next, the film fluid of the first pigment stoste is supplied with the second pigment stoste of supplying with from the second stoste supply unit y shown in Figure 2, in the thin layer that is formed between shaft collar A and the rotating disc B, mix the first pigment stoste and the second pigment stoste and separate out pigment particle.Reclaim the pigment particle separate out to be dispersed in the dispersible pigment dispersion in the aqueous medium as pigment particle at liquid discharge portion z.

The first pigment stoste of using in the preparation of dispersible pigment dispersion is preferably water or alkaline aqueous solution.As alkaline aqueous solution, can enumerate ammoniacal liquor, sodium hydrate aqueous solution and potassium hydroxide aqueous solution.

The second pigment stoste of using in the preparation of dispersible pigment dispersion is used the pigment solution that is dissolved with pigment in solvent.As long as be used for the solvent of dissolving pigment can dissolve well pigment then without particular limitation of.As the suitable example of the solvent that dissolves pigment, can enumerate organic solvent or acidic aqueous solution, but be preferably acidic aqueous solution.As the concrete example of acidic aqueous solution, can enumerate sulfuric acid, hydrochloric acid, nitric acid and trifluoroacetic acid, particularly preferably the strong acid such as the concentrated sulphuric acid of working concentration more than 95%.

As mentioned above, method of adjustment as dispersible pigment dispersion, preferred acid molten (アシッドペースティ Application グ) method, the method is mixed the acidic aqueous solution (the second pigment stoste) of pigment and is separated out pigment particle with water or alkaline aqueous solution (the first pigment stoste).

As the method beyond the molten method of acid, also preferably use the organic solvent solution with pigment to use as the second pigment stoste, the poor solvent of pigment is used the method for mixing the first pigment stoste and the second pigment stoste and pigment being separated out as the first pigment stoste.As the suitable example that is included in the organic solvent in the second pigment stoste, can enumerate the non-proton property polar organic solvents such as METHYLPYRROLIDONE, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide and sulfolane.As the suitable example of the poor solvent that is used as the first pigment stoste, can enumerate water, methyl alcohol, ethanol, methanol aqueous solution and ethanol water.

Crystal formation when separating out for control pigment and the purpose of crystallite size also can be added known organic solvent, macromolecular compound and surfactant in above-mentioned the first pigment stoste and the second pigment stoste.

Also can be at alkaline aqueous solutions such as the liquid discharge portion z hybrid pigment dispersion liquid that reclaims dispersible pigment dispersion and sodium hydrate aqueous solutions.By carrying out this processing, can make the surface hydrophilic of pigment particle.The pigment particle of hydrophiling is easy to disperse well when using surfactant.Therefore, by making the pigment particle hydrophiling, be easy to obtain the dispersion liquid of the pigment particle of dispersion stabilization excellence.

The quantity delivered of the first pigment stoste changes according to the shape of microreactor, but typically is preferably more than 100ml/ minute below 1000ml/ minute.The quantity delivered of the second pigment stoste changes according to the quantity delivered of the first pigment stoste, but typically is preferably more than 1ml/ minute below 500ml/ minute.Temperature during the supply of the first pigment stoste and the second pigment stoste is according to the pigment stoste of using and different, but is generally more than 0 ℃ below 50 ℃.

Can reduce by the quantity delivered that improves the back pressure that applies from the upside of shaft collar A, improves the rotational speed of rotating disc B or reduce the second pigment stoste the Cv value of pigment particle.

More than to using microreactor to mix the first pigment stoste and the second pigment stoste and pigment particle being separated out and the method that obtains dispersible pigment dispersion is illustrated, but also can use the multiple pigment stoste of mixing the synthesis material comprise pigment, and the method that the pigment that generates through their chemical reaction is separated out as particulate obtains dispersible pigment dispersion.As the concrete example of this method, can enumerate and mix the pigment stoste comprise diazo salt and the pigment stoste that comprises coupling agent, the method that the particulate of AZO pigments is separated out.

As mentioned above, the average primary particle diameter of the pigment particle that contains in dispersible pigment dispersion is below the 50nm, and the Cv value is less than 20%, and average roundness is more than 0.900.Use as raw material by the dispersion liquid that will comprise this pigment particle, be easy to prepare shape evenly and the precipitous developing toner for electrostatic latent images of particle diameter distribution.

The average primary particle diameter of pigment particle and Cv value can be tried to achieve by the size-grade distribution of using the devices such as particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure pigment particle.The average roundness of pigment particle can be tried to achieve according to the TEM image of pigment particle.

(cohesion of particulate)

Use the dispersion liquid of the particulate of said method preparation to consist of the particle coagulation body with the mode appropriate combination that contains predetermined component in the toner.As the suitable method that makes particle coagulation, can enumerate the method for in the aqueous medium dispersion liquid of particulate, adding polycoagulant.

As the example of polycoagulant, can enumerate inorganic metal salt, inorganic ammonium salt, the above metal complex of divalence.As inorganic metal salt, can enumerate slaine and the inorganic metal salt polymkeric substance such as polyaluminium chloride and poly-aluminium hydroxide such as sodium sulphate, sodium chloride, lime chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and aluminium sulphate.As inorganic ammonium salt, can enumerate ammonium sulfate, ammonium chloride and ammonium nitrate.The cationic surfactant of quaternary and polyethyleneimine also can be used as polycoagulant and use.

Preferably use divalent metal salt and univalent metal salt as polycoagulant.Preferably use simultaneously divalent metal salt and univalent metal salt.Divalent metal salt, therefore when using them simultaneously, is easy to control the particle diameter of gained particle coagulation body, and makes easily size-grade distribution precipitous because the cohesion speed of particulate is different from univalent metal salt.

The addition of polycoagulant in the scope that does not hinder the object of the invention without particular limitation of, with respect to the solid constituent of particle dispersion liquid, be preferably below the above 10mmol/g of 0.1mmol/g.The addition of polycoagulant is preferably suitably adjusted according to the kind and the amount that are included in the surfactant in the particle dispersion liquid.

Being added on after the pH that adjusts particle dispersion liquid of polycoagulant carried out under the temperature below the glass transition temperature of binding resin.When binding resin is vibrin, adjust to alkaline side at the pH with particle dispersion liquid especially, preferably adjust to the above polycoagulant that adds afterwards of pH10.When making in this way, can make the particle diameter of particle coagulation body distribute precipitous by particulate is condensed equably.Polycoagulant can add once, also can add one by one.

Preferably after proceeding to the particle diameter that the particle coagulation body becomes expectation, cohesion adds the cohesion terminator.As the example of cohesion terminator, can enumerate sodium chloride and NaOH.So can access the particle coagulation body.

[(II) shape control operation]

In (II) shape control operation, make the composition polymerization that is included in the particle coagulation body that obtains by (I) cohesion process, and control the shape of resulting toner.

In (II) shape control operation, temperature when the aqueous medium dispersion liquid of heated particulate condensed matter is preferably more than the glass transition temperature of binding resin, below the fusing point of binding resin, more preferably more than the glass transition temperature of binding resin+10 ℃, below the fusing point of binding resin.By the dispersion liquid in the aqueous medium of particle coagulation body being heated to the temperature of above-mentioned scope, can be included in well the polymerization of the composition in the particle coagulation body, be easy to prepare the toner of suitable spheroidization degree.

When the aqueous medium dispersion liquid of heated particulate condensed matter, the shape of particle coagulation body moves closer to sphere.Temperature and time in the time of can heating by control is controlled to be the spheroidization degree of particle the value of expectation.This is because along with the melt viscosity of temperature rising binding resin descends, under capillary effect to the reason of the change of shape of the direction generation particle of spheroidization.The preferable range of spheroidization degree is more than 0.965 below 0.985.The spheroidization degree for example can use " FPIA3000 " (Sysmex company (シスメッ Network Co., Ltd.) system) to measure.So can access the dispersion liquid of the toner particle of the particle diameter of expectation and shape.

Use any means to reclaim the toner particle that obtains by (II) shape control operation, and in various image processing systems, suitably be used as toner.

[(III) matting]

As required, water cleans the toner particle that obtains in (II) shape control operation in (III) matting.Cleaning method without particular limitation of, for example can enumerate from the dispersion liquid of toner particle and reclaim toner particle as wet cake through Separation of Solid and Liquid, the method of water cleaning gained wet cake precipitates with the toner particle in the dispersion liquid that makes toner particle, and with supernatant and water displacement, the method that toner particle is dispersed in water again.

[(IV) drying process]

As required, the dry toner particle that in (II) shape control operation, obtains in (IV) drying process.The method of dry toner particle without particular limitation of.As suitable drying means, can enumerate the method for dryers such as using spray dryer, fluid bed dryer, vacuum freezing exsiccator or pressure Reduction Dryer.In these methods, consider from the aspect of the cohesion that is easy to suppress the toner particle the drying, more preferably use the method for spray dryer.When using spray dryer, can spray to the dispersion liquid of the external additives such as silicon dioxide by the dispersion liquid with toner particle, thereby make external additive be attached to the surface of toner particle.

[(V) the outside operation of adding]

The developing toner for electrostatic latent images that uses method of the present invention to prepare can also be for there being the material of external additive as required in its surface attachment.Make external additive be attached to toner particle the surface method without particular limitation of.As suitable method, can enumerate mixers such as using Henschel mixer and nauta mixer, regularization condition also mixes so that external additive does not bury the method in toner surface.

According to method of the present invention described above, can provide the preparation method of toner of the excellent storage stability under low-temperature fixability and the high temperature and the toner that uses this preparation method to obtain.Therefore, use the developing toner for electrostatic latent images of method preparation of the present invention to be adapted at using in the various image processing systems.

Embodiment

Below, by embodiment the present invention is carried out more specific description.In addition, the present invention be not implemented the example scope limit.

(formulation example 1)

(preparation of binding resin dispersion liquid)

Prepare in accordance with the following methods the binding resin dispersion liquid.

Use following amorphous polyester resin as binding resin.

Monomer composition: polyoxypropylene (2,2)-2, two (4-hydroxy phenyl) propane/polyoxyethylene (2,0)-2 of 2-, two (4-hydroxy phenyl) propane/fumaric acid of 2-/trimellitic acid=25/25/46/4(mol ratio)

Number-average molecular weight (Mn): 2500

Weight-average molecular weight (Mw): 6500

Molecular weight distribution (Mw/Mn): 2.6

Softening point: 91 ℃

Glass transition temperature (Tg): 51 ℃

Acid value: 15.5mgKOH/g

To use turbine grinder T250(ターボ Industrial Co., Ltd system) coarse crushing thing 100 mass parts, anionic surfactant (エマー Le E27C about the mean grain size 10 μ m that obtain of coarse crushing binding resin, Kao Corp's system) 2 mass parts and 0.1N-sodium hydrate aqueous solution (alkaline matter) 50 mass parts are mixed, and then ion exchange water are added as aqueous medium and the preparation total amount is the slurry of 500 mass parts.The slurry that obtains is dropped in the withstand voltage round bottom rustless steel container, use high speed shear emulsifier unit Clearmix(Network レアミッ Network ス, CLM-2.2S, エ system テ Network ニッ Network Co., Ltd. system), be forced into 145 ℃, pressure 0.5MPa(G in that slurry is heated) state under, carry out shearing in 30 minutes with the rotor revolution number of 20000r/min and disperse.Afterwards, cool off slurry with 5 ℃/minute speed and obtain binding resin dispersion liquid R-1 until the temperature in the rustless steel container becomes 50 ℃ of rotor revolution number continuation stirrings with 15000r/min.

(formulation example 2)

(preparation of mould release dispersion liquid)

Prepare in accordance with the following methods the mould release dispersion liquid.

With mould release (WEP-5, behenic acid pentaerythrite ester type waxes (ペ Application タエリスリトー Le ベヘ Application acid エステ Le ワッ Network ス), 84 ℃ of melt temperatures, NOF Corp's system) 200 mass parts, anionic surfactant (エマー Le E27C, Kao Corp's system) 2 mass parts and ion exchange water 800 mass parts are mixed, be heated to 100 ℃ and make after the mould release melting, carry out emulsification in 5 minutes with homogenizer (ウ Le トラタラッ Network ス T50, IKA company system).Then, use high voltage type homogenizer (Na ノマイザー NV-200, the industrial Co., Ltd. of Jitian's machinery system), press under the condition of 100MPa at 120 ℃, ejection, carry out second emulsifying and process.In the high voltage type homogenizer, the diameter of plunger of pressure head is made as φ 10mm, and 120 microns through nozzle is used as generator.So, obtaining mean grain size is that 250nm, fusing point are that 83 ℃, solid component concentration are the mould release dispersion liquid W-1 of 20 quality %.

(embodiment 1)

(preparation of dispersible pigment dispersion)

Use pressure film reactor (ULREA SS-11, エ system テ Network ニッ Network Co., Ltd. system) as microreactor, use sour molten method pigment preparation dispersion liquid.

As the second pigment stoste, green pigment (C.I. pigment blue 15: the 3(copper phthalocyanine)) is dissolved in the concentrated sulphuric acid (98%), obtain 3% copper phthalocyanine/98% concentrated sulfuric acid aqueous solution.

Set as shown below the device condition of microreactor, water is used as the first pigment stoste, supply with the first pigment stoste from the first stoste supply unit x under the following conditions, supply with the second pigment stoste from the second stoste supply unit y under the following conditions.

＜device condition 〉

Process supply pressure: 0.3MPa

Back pressure: 0.02MPa

Disc spin speed: 1700rpm

The＜the first stoste supply unit condition 〉

Fluid temperature: 5 ℃

Flow: 400ml/ minute

The＜the second stoste supply unit condition 〉

Flow: 3ml/ minute

Then, for the pigment particle that obtains, flow into 6N-NaOH aqueous solution with 10 ℃ of flow 24ml/ minutes, fluid temperature at the liquid discharge portion z with cooling jacket.Under the condition of 10 ℃ of chuck cooling water temperatures, rapid mixing pigment particle and NaOH aqueous solution, thus carry out to the importing processing of the hydrophilic radical on pigment particle surface.

Use stirring apparatus (THREE-ONE MOTOR(スリーワンモーター) Type600G, new eastern science Co., Ltd. system), agitator: impeller type), under the condition of peripheral speed 1m/ second, the incorporation time 2 hours of agitator, 20 ℃ of jacket temperatures, the mixed liquor that obtains is stirred, form at pigment particle under the state of soft condensed matter, use film filter (aperture 1 μ m) from the wet cake of mixed liquor leaching pigment particle.Afterwards, the wet cake of the pigment particle of leaching and the lauryl sodium sulfate aqueous solution of 0.5 quality % are dropped among the Network レアミッ Network ス (エ system テ Network ニッ Network Co., Ltd. system), carry out with the rotational speed of 20000rpm 5 minutes pigment particle again dispersion and obtain dispersible pigment dispersion P-1.

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) that the size-grade distribution of the pigment particle of the dispersible pigment dispersion that obtains is measured.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 22nm, and the Cv value of size-grade distribution is 13%.According to the TEM image confirming of pigment particle circularity be 0.940.Cv value, circularity are tried to achieve according to following formula.The Cv value refers to target value for the expression particle diameter distribution width, and the Cv value is less, and the expression particle diameter distributes more precipitous.

Cv value=100 * standard deviation/volume average particle size

Circularity=4 π S/L ²(S: area, L: circumferential length)

(cohesion process)

In the round-bottomed flask container of the capacity 2L of stainless steel, put into the mould release particle dispersion liquid W-1 of binding resin dispersion liquid R-1,50g of 425g and the dispersible pigment dispersion P-1 of 50g, at 25 ℃ of lower these materials that mix.Then, using under the state of paddle with the content of the speed stirred flask of 200rpm, in flask, adding 1N-sodium hydrate aqueous solution 1g.Afterwards, after the content of 25 ℃ of lower stirred flask 10 minutes, added polycoagulant (the magnesium chloride hexahydrate aqueous solution of concentration 50.0 quality %) 30g with 5 minutes in the clockwise flask.After adding polycoagulant, with 0.2 ℃/minute programming rate temperature in the flask is promoted to 50 ℃, synthermal lower, the content of stirred flask 30 minutes is so that particle coagulation.Afterwards, in flask, add the sodium-chloride water solution 50g of concentration 20 quality %, thereby stop the cohesion of particulate, obtain the dispersion liquid of particle coagulation body.

(shape control operation)

Dispersion liquid to the particle coagulation body that obtains adds 5% lauryl sodium sulfate aqueous solution 100g, with 0.2 ℃/minute programming rate the dispersion liquid of particle coagulation body is warming up to 65 ℃ from 50 ℃, synthermal lower, stir the dispersion liquid 1 hour of particle coagulation body, thereby make the polymerization of particle coagulation body and be controlled to be the shape of toner spherical.Afterwards, make temperature decline in the flask with 10 ℃/minute speed, make the interior temperature of flask become 25 ℃.At this moment, the volume average particle size that is included in the toner particle in the toner dispersion liquid in the flask is 5.5 μ m, and the spheroidization degree is 0.978.

(matting)

Attract to filter toner dispersion liquid, the wet cake of leaching toner.Wet cake is dispersed in the ion exchange water again and cleans toner.Repeat same operation, clean toner makes the toner of recovery for 5 times afterwards by subsequent processing wet cake drying.

(drying process)

The wet cake of toner is dispersed in the ethanol water that concentration is 50 quality % with the preparation slurry.Use continous way surface modification device (Coatmizer(コートマイザー), Off ロイ Application ト Industry Co., Ltd system)) make the slurry drying that obtains obtain toner.When drying, the alcohol dispersion liquid of silicon dioxide that will comprise with respect to the quality of toner the silicon dioxide of 0.2 quality % is sprayed with the dispersion liquid of toner, makes silicon dioxide be attached to the surface of toner as external additive.Use the drying condition of コートマイザー to be 45 ℃ of hot blast temperatures, pressure fan air quantity 2m ³/ minute.

(the outside operation of adding)

Dried powder 100 mass parts and hydrophobic silica (the Japanese アエ of REA-90(ロジ Le Co., Ltd. system) using Henschel mixer (Mitsui three pond Industrial Co., Ltd systems) to be blended in to obtain in the drying process) 2 mass parts 5 minutes, (sieve aperture 48 μ m) sieve with the #300 order, obtain the toner of embodiment 1.

For the toner of the embodiment 1 that so obtains, use particle size distribution device (micro-track(マイ Network ロトラッ Network) UPA150, Nikkiso Company Limited's system), measure volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 5.5 μ m, spheroidization degree are 0.978, the MV/MN value is 1.2.

The toner that use is obtained by embodiment 1 is estimated in accordance with the following methods particle diameter and is distributed and the carried charge distribution.The evaluation result of the toner of embodiment 1 is remembered in table 2.

＜particle diameter distributes 〉

As the evaluation of particle diameter distribution, according to the MV/MN value of following standard evaluation toner.

Zero: the MV/MN value is below 1.5.

*: the MV/MN value is greater than 1.5.

＜carried charge distributes 〉

(preparation of carrier)

An amount of each starting material that cooperate are scaled 9.9mol%, Fe so that MnO is scaled 39.7mol%, MgO ₂O ₃Be scaled 49.6mol%, SrO is scaled 0.8mol%, adds water, pulverize and mixed 10 minutes with wet ball mill.The potpourri that obtains is carried out after the drying, 950 ℃ of lower maintenances 4 hours.Then, with wet ball mill crushed mixture 24 hours with the preparation slurry.Slurry is carried out after granulation and the drying, in the atmosphere of oxygen concentration 2%, kept granules 6 hours down at 1270 ℃, separate afterwards broken and granularity adjustment and obtain manganese based ferrite particle (carrier core).The mean grain size of the manganese based ferrite particle that obtains is 35 μ m, and the magnetic field that applies is 3000(10 ³/ 4 π A/m) saturated magnetization the time is 70Am ²/ kg.

Then, by methyl ethyl ketone dilution polyamide-imide resin (trimellitic anhydride and 4,4 '-multipolymer of diaminodiphenyl-methane) the preparation resin solution, next tetrafluoroethene hexafluoropropylene copolymer (FEP) and silicon dioxide (2 quality % of resin total amount) are scattered in the resin solution, obtain being scaled with solid constituent the carrier masking liquid 1kg of the amount of 150g.The mass ratio of polyamide-imide resin and FEP is that polyamide-imide resin/FEP is 2/8, and the solid constituent ratio of resin solution is 10 quality %.

Use thermopnore coating unit (スピラコータ SP-25, field, ridge Jinggong Co., Ltd system) to coat Mn ferrite particle 10kg with resulting carrier masking liquid.Afterwards, will be burnt till under 220 ℃ 1 hour by the manganese based ferrite particle of resin-coating, obtaining the resin-coating amount is the resin-coating ferrite carrier of 3 quality %.

(preparation of two-component developing agent)

The toner of the resin-coating ferrite carrier that obtains and embodiment 1 dropped into take off the step and strangle mixer (ター Block ラミキサー, the シ of Co., Ltd. Application マ Le エンタープライゼス system) so that the toner concentration in the two-component developing agent becomes 7 quality %, mixed 5 minutes, the two-component developing agent of usefulness is estimated in preparation.

As evaluating apparatus, use color printer (FS-C5400DN, Kyoji, Meida K.K's system).The two-component developing agent 3g that obtains is packed in the rotatable magnetic roller, make the magnetic roller with the speed rotation of 500rpm, and make the cylinder type electrode contraposition configuration that has the interval of gap 5mm with the magnetic roller, recovery is with the toner layer of electric field intensity 1kV/cm electrolytic separation, the toner layer that reclaims is dropped into E-spart analyser (イースパートア Na ライザ, the EST-II type, ホソカワミ Network ロ Application Co., Ltd. system) in, the average band electric weight X(μ C/g of mensuration toner).According to the average band electric weight X(μ C/g that measures) carry out the evaluation that carried charge distributes with standard deviation y according to following formula.

○：y≤3.5×X

×：y＞3.5×X

(embodiment 2)

(preparation of dispersible pigment dispersion)

As the second pigment stoste, magenta pigment (C.I. pigment red 122) is dissolved in dimethyl sulfoxide (DMSO)/potassium hydroxide mixed liquor, obtain the mixing dirty solution of the 8N-potassium hydroxide aqueous solution of 2% quinacridone magenta pigment/82% dimethyl sulfoxide (DMSO)/16%.

Set as shown below the device condition of microreactor, water is used as the first pigment stoste, under following condition, supply with the first pigment stoste from the first stoste supply unit x, under following condition, supply with the second pigment stoste from the second stoste supply unit y.

＜device condition 〉

Process supply pressure: 0.3MPa

Back pressure: 0.02MPa

Disc spin speed: 1500rpm

The＜the first stoste supply unit condition 〉

Fluid temperature: 20 ℃

Flow: 400ml/ minute

The＜the second stoste supply unit condition 〉

Flow: 3ml/ minute

The pH of the dispersion liquid of the pigment particle that obtains at liquid discharge portion z is 11.6.Then, use stirring apparatus (スリーワンモーター Type600G, new eastern science Co., Ltd. system, agitator: impeller type), under the condition of peripheral speed 1m/ second, the incorporation time 2 hours of agitator, 20 ℃ of jacket temperatures, stir the dispersion liquid of resulting pigment particle, under the state of the soft condensed matter that forms pigment particle, use film filter (aperture 1 μ m) wet cake of leaching pigment particle from mixed liquor.Afterwards, wet cake and the 0.5 quality % lauryl sodium sulfate aqueous solution of the pigment particle of leaching are dropped among the Network レアミッ Network ス (エ system テ Network ニッ Network Co., Ltd. system), under rotational speed 20000rpm, 5 minutes condition, carry out the again dispersion of pigment particle, obtain dispersible pigment dispersion P-2.

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure the size-grade distribution of the pigment particle of resulting dispersible pigment dispersion.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 13nm, and the Cv value of size-grade distribution is 17%.TEM image confirming circularity according to pigment particle is 0.970.

(cohesion process, shape control operation, matting, drying process and the outside operation of adding)

Cohesion process, shape control operation, matting, drying process and outside the interpolation in the operation, use the dispersible pigment dispersion P-2 except replacing dispersible pigment dispersion P-1, other similarly to Example 1, thereby obtain the toner of embodiment 2.

For the toner of the embodiment 2 that obtains, measure similarly to Example 1 volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 5.5 μ m, spheroidization degree are 0.975, the MV/MN value is 1.2.

The toner that use is obtained by embodiment 2 is estimated similarly to Example 1 particle diameter distribution and carried charge and is distributed.The evaluation result of toner is remembered in table 2.

(embodiment 3)

(preparation of dispersible pigment dispersion)

As microreactor, use and force film reactor (ULREA SS-11, エ system テ Network ニッ Network Co., Ltd. system), except the device condition being changed to following condition, other use sour molten method pigment preparation dispersion liquid P-3 similarly to Example 1.When the pigment preparation dispersion liquid, the hydrophilic radical importing processing of NaOH aqueous solution and the again dispersion treatment of pigment particle have been carried out similarly to Example 1 using.

＜device condition 〉

Process supply pressure: 0.3MPa

Back pressure: 0.04MPa

Disc spin speed: 2500rpm

The＜the first stoste supply unit condition 〉

Fluid temperature: 25 ℃

Flow: 400ml/ minute

The＜the second stoste supply unit condition 〉

Flow: 3ml/ minute

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure the size-grade distribution of the pigment particle of resulting dispersible pigment dispersion.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 46nm, and the Cv value of size-grade distribution is 18%.TEM image confirming circularity according to pigment particle is 0.955.

Cohesion process, shape control operation, matting, drying process and outside the interpolation in the operation, use the dispersible pigment dispersion P-3 except replacing dispersible pigment dispersion P-1, other similarly to Example 1, thereby obtain the toner of embodiment 3.

For the toner of the embodiment 3 that obtains, measure similarly to Example 1 volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 5.7 μ m, spheroidization degree are 0.973, the MV/MN value is 1.3.

The toner that use is obtained by embodiment 3 is estimated similarly to Example 1 particle diameter distribution and carried charge and is distributed.The evaluation result of toner is remembered in table 2.

(comparative example 1)

(preparation of dispersible pigment dispersion)

To mix as green pigment (C.I. pigment blue 15: the 3(copper phthalocyanine)) 90 mass parts, anionic surfactant (lauryl sodium sulfate) 10 mass parts and ion exchange water 400 mass parts of pigment, use impacting with high pressure formula dispersion machine ア Le ティマイザー (HJP30006, the スギノマシ of Co., Ltd. Application system), carry out emulsification in 1 hour and dispersion, obtain dispersible pigment dispersion P-4.

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure the size-grade distribution of the pigment particle of resulting dispersible pigment dispersion.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 160nm, and the Cv value of size-grade distribution is 25%.TEM image confirming circularity according to pigment particle is 0.800.

Cohesion process, shape control operation, matting, drying process and outside the interpolation in the operation, use the dispersible pigment dispersion P-4 except replacing dispersible pigment dispersion P-1, other similarly to Example 1, thereby obtain the toner of comparative example 1.

For the toner of the comparative example 1 that obtains, measure similarly to Example 1 volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 6.5 μ m, spheroidization degree are 0.96, the MV/MN value is 2.4.

The toner that use is obtained by comparative example 1 is estimated similarly to Example 1 particle diameter distribution and carried charge and is distributed.The evaluation result of toner is remembered in table 2.

(comparative example 2)

Except magenta pigment (C.I. pigment red 122) was used as pigment, other and comparative example 1 were same, thereby obtained the dispersible pigment dispersion P-5 for comparative example 2.

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure the size-grade distribution of the pigment particle of resulting dispersible pigment dispersion.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 180nm, and the Cv value of size-grade distribution is 29%.TEM image confirming circularity according to pigment particle is 0.820.

Cohesion process, shape control operation, matting, drying process and outside the interpolation in the operation, use the dispersible pigment dispersion P-5 except replacing dispersible pigment dispersion P-1, other similarly to Example 1, thereby obtain the toner of comparative example 2.

For the toner of the comparative example 2 that obtains, measure similarly to Example 1 volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 6.5 μ m, spheroidization degree are 0.96, the MV/MN value is 2.2.

The toner that use is obtained by comparative example 2 is estimated similarly to Example 1 particle diameter distribution and carried charge and is distributed.The evaluation result of toner is remembered in table 2.

(comparative example 3)

Use sour molten method, the pigment preparation dispersion liquid.

Green pigment (C.I. pigment blue 15: the 3(copper phthalocyanine)) is dissolved in the concentrated sulphuric acid (98%), 3% copper phthalocyanine/98% concentrated sulfuric acid aqueous solution is dropped into stirring apparatus (スリーワンモーター Type600G with the water limit of the 1L of 10 ℃ of temperature, new eastern science Co., Ltd. system, agitator: stir with the peripheral speed 1m/ of agitator second on the limit impeller type).

Carry out second with the peripheral speed 1m/ of agitator adding the 6N-NaOH aqueous solution after 30 minutes the stirring, the pigment mixed liquor has neutralized.

Further under the condition of peripheral speed 1m/ second, the incorporation time 2 hours of agitator, 20 ℃ of jacket temperatures, stir resulting mixed liquor, form at pigment particle under the state of soft condensed matter, use film filter (aperture 1 μ m) wet cake of leaching pigment particle from mixed liquor.Afterwards, wet cake and the 0.5 quality % lauryl sodium sulfate aqueous solution of the pigment particle of leaching are dropped among the Network レアミッ Network ス (エ system テ Network ニッ Network Co., Ltd. system), under rotational speed 20000rpm, 5 minutes condition, carry out the again dispersion of pigment particle, and obtain dispersible pigment dispersion P-6.

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure the size-grade distribution of the pigment particle of resulting dispersible pigment dispersion.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 45nm, and the Cv value of size-grade distribution is 20%.TEM image confirming circularity according to pigment particle is 0.860.

Cohesion process, shape control operation, matting, drying process and outside the interpolation in the operation, use the dispersible pigment dispersion P-6 except replacing dispersible pigment dispersion P-1, other similarly to Example 1, thereby obtain the toner of comparative example 3.

For the toner of the comparative example 3 that obtains, measure similarly to Example 1 volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 6.5 μ m, spheroidization degree are 0.972, the MV/MN value is 2.3.

The toner that use is obtained by comparative example 3 is estimated similarly to Example 1 particle diameter distribution and carried charge and is distributed.The evaluation result of toner is remembered in table 2.

(comparative example 4)

(preparation of dispersible pigment dispersion)

As microreactor, use and force film reactor (ULREA SS-11(エ system テ Network ニッ Network Co., Ltd. system)), except the device condition being changed to following condition, other use sour molten method pigment preparation dispersion liquid P-7 similarly to Example 1.When the pigment preparation dispersion liquid, use similarly to Example 1 the hydrophilic radical importing processing of NaOH aqueous solution and the again dispersion treatment of pigment particle.

＜device condition 〉

Process supply pressure: 0.3MPa

Back pressure: 0.08MPa

Disc spin speed: 3500rpm

The＜the first stoste supply unit condition 〉

Fluid temperature: 40 ℃

Flow: 400ml/ minute

The＜the second stoste supply unit condition 〉

Flow: 5ml/ minute

Use particle size distribution device (マイ Network ロトラッ Network UPA150, Nikkiso Company Limited's system) to measure the size-grade distribution of the pigment particle of resulting dispersible pigment dispersion.The volume average particle size of the pigment particle of the dispersible pigment dispersion that obtains is 62nm, and the Cv value of size-grade distribution is 23%.TEM image confirming circularity according to pigment particle is 0.958.

Cohesion process, shape control operation, matting, drying process and outside the interpolation in the operation, use the dispersible pigment dispersion P-7 except replacing dispersible pigment dispersion P-1, other similarly to Example 1, thereby obtain the toner of comparative example 4.

For the toner of the comparative example 4 that obtains, measure similarly to Example 1 volume average particle size MV, spheroidization degree and MV/MN value.Volume average particle size MV is that 6.3 μ m, spheroidization degree are 0.969, the MV/MN value is 2.2.

The toner that use is obtained by comparative example 4 is estimated similarly to Example 1 particle diameter distribution and carried charge and is distributed.The evaluation result of toner is remembered in table 1.

Below, for the pigment that in embodiment 1～3 and comparative example 1～4, is included in for the dispersible pigment dispersion of the preparation of toner, volume average particle size, Cv value and circularity are remembered in table 1.In table 1, about pigment, CP represents that (the C.I. pigment blue 15: 3), QM represents quinacridone pinkish red (C.I. pigment red 122) to copper phthalocyanine.In table 1, about device, A is for forcing film reactor (ULREA SS-11, エ system テ Network ニッ Network Co., Ltd. system), B is impacting with high pressure formula dispersion machine ア Le ティマイザー (HJP30006, the スギノマシ of Co., Ltd. Application system), and C is stirring apparatus (スリーワンモーター Type600G, new eastern science Co., Ltd. system, agitator: impeller type).

[table 1]

[table 2]

Comprising as can be known average primary particle diameter according to table 1 and table 2 is below the 50nm, and the Cv value is less than 20%, and average roundness is that the particle diameter of developing toner for electrostatic latent images of the embodiment 1～3 of the pigment particle more than 0.900 distributes and carried charge distributes precipitous.

On the other hand as can be known, the particle diameter distribution and the carried charge wider distribution that comprise the toner of the comparative example 1～4 of the pigment particle of at least one disengaging specialized range in average primary particle diameter, Cv value and the average roundness.

Claims

1. developing toner for electrostatic latent images, at least comprise binding resin, pigment particle and mould release, by the particle coagulation that comprises the composition that consists of developing toner for electrostatic latent images is obtained after the particle coagulation body, make the polymerization of described particle coagulation body and obtain, the average primary particle diameter of described pigment particle is below the 50nm, the Cv value is less than 20%, and average roundness is more than 0.900.

2. developing toner for electrostatic latent images according to claim 1 uses microreactor, mixes the first pigment stoste and the second pigment stoste and pigment is separated out and obtains described pigment particle, and described microreactor comprises:

Shaft collar (A) and rotating disc (B) for discoid two dishes, are configured to form thin layer between the circular face of two dishes;

3. developing toner for electrostatic latent images according to claim 2, the thickness of the thin layer between the circular face of described two dishes are below the above 100 μ m of 1 μ m.

4. developing toner for electrostatic latent images according to claim 2, described the first pigment stoste is pigment solution, described the second pigment stoste is water or alkaline aqueous solution.

5. developing toner for electrostatic latent images according to claim 4, described the first pigment stoste is the acidic aqueous solution of pigment.